Water-insoluble thiadiazole containing monoazo dyes

ABSTRACT

N,N-substituted para-aminomonoazo dyes having a 3-( Beta carbalkoxyethyl)-mercapto-5-aminothiadiazole-(1,2,4) as diazo component. They are useful for dyeing cellulose esters or synthetic linear polyesters.

United States Patent [52] U.S.CI 260/158,

[51] int. Cl ..C09b29/08,

[50] Field at Search 2611/1521 [56] References Cited UNITED STATES PATENTS 3,441,554 4/1969 Hahn et a1. 260/158 Primary Exan iinercharles B. Parker 1 Assistant Examiner-.-Dona1d M. Papuga Attorney-Johnston, Root, OKeefie, Keil, Thompson &

[72] Inventors Erwin Hahn Viernheim; Hans Guenter Wlppel, Ludwlgshalen, both of Germany [2|l Appl. No. 859,204 [22] Filed Sept. 18, 1969 [45] Patented Nov. 16, 1971 [73] Assignee Badische Anilin- & Soda-Fabrik Aktiengesellschalt Ludwigshaien am Rhine, Germany i [32] Priority Sept. 21, 1968 T [3 3] Germany [31] P1794201.7

[54] WATER-INSOLUBLE THIADIAZOLE CONTAINING MONOAZO DYES 2 Claims, N0 Drawings Shurtleff ABSTRACT: N,N-substituted para-aminomonoazo dyes having a 3-(B-carbalkoxyethyl)-mercapto-5-aminothiadiazole- (1,2,4) as diazo component. They are useful for dyeing cellulose esters or synthetic linear polyesters.

WATER-INSOLUBLE THIADIAZOLE CONTAINING MONOAZO DYES The invention relates to water-insoluble monoazo dyes having the general formula (I):

in which R and R denote alkyl radicals having one to four carbon atoms, X denotes a hydrogen atom or a methoxy or ethoxy group, Y denotes a hydrogen, chlorine or bromine atom or a methyl, ethyl, methoxy, ethoxy, acetylamino or propionylamino group and n denotes one of the integers l and Examples of the radicals R and R are methyl, ethyl, npropyl, isopropyl, n-butyl, isobutyl or tertiary-butyl.

Dyes having the general formula:

in which Z denotes a hydrogen or chlorine atom or a methyl group, and R, R and n have the meanings given above are of special industrial importance.

The new dyes are eminently suitable, particularly in finely divided form, for dyeing textile material of acetylcellulose, such as secondary acetate or triacetate, polyamides, such as nylon-6 or nylon-6,6, and particularly linear polyesters such as polyethylene glycol terephthalate.

The dyeings obtained have good wet-fastness, good lightfastness and very good thermal resistance. The very good levelling property of the new dyes should also be emphasized.

The carrier method and preferably the high-temperature method and the thermosol method are suitable dyeing methods.

Dyes having the formula (I) may be obtained for example by reaction of a diazo compound of an amine having the general formula (II):

S (II) with a coupling component having the general formula (Ill):

Y (CHM-CO 0R (III) in which R, X, Y and n have the meanings given above.

Examples of compounds having the formula (ll) are: 3-(B-carbomethoxyethyl)-mercapto-5-aminothiadiazolel 3, 3-(fi-carboethoxyethyl)-mercapto-5-aminothiadiazole- S-(B-carbo-n-butoxyethyl)-mercapto-5-aminothiadiazole- 3-(B-carboisopropoxylethyl)-mercapto-5 -aminothiadiazole- (1,2,4).

Examples of compounds having the formula (lll) are: N-benzyl-N-B-carbomethoxyethylaniline, N-benzyl-N-carboethoxyethylaniline, N-B-phenylethyl-N-fl-carboethoxyethylaniline, N-B-phenylethyl-N-Bcarbomethoxyethyl-m-toluidine, N-B-phenylethyl-N-B-carboethoxyethyl-m-chloroaniline, N-benzyl-N-fl-carbomethoxyethyl-m-acetylaminoaniline, N-benzyl-N-B-carboethoxyethyl-3-acetylamino-6-methoxyaniline, N-benzyl-N-B-carbobutoxyethyl-m-toluidine, N-benzyl-N-B-carbomcthoxyethyl-m-chloroaniline and N-benzyl-NB-carbopropoxyethylaniline.

The invention is illustrated by the following examples. The parts and percentages given in the following examples are by weight.

EXAMPLE I l 1.9 parts of 3-B-carbomethoxyethylmercapto-S- aminothiadiazole is dissolved at room temperature in 30 parts of concentrated sulfuric acid. One hundred parts of a mixture in the ratio 17:3 of acetic acid and propionic acid is allowed to flow gradually into this solution at 0 to 5 C. Then at the same temperature 15 parts of nitrosylsulfuric acid having a content of 12.8 percent of free 57 trioxide is added. The whole is stirred for 3 hours at 0 to 5 C. and the clear diazo solution obtained is allowed to flow into a solution of l4. l5 parts of N- benzyl-N-B-carboethoxyethylaniline in 250 parts of acetone, 10 parts of concentrated hydrochloride acid and 75 parts of ice. Thirty minutes later the resulting mixture is diluted by adding l ,000 parts of ice.

The dye which separates in crystalline form is suction filtered after stirring has been continued for 10 hours, washed with water until neutral and dried at 50 C. at subatmospheric pressure. It dyes polyethylene glycol terephthalate bright red shades having very good light-fastness and thermal resistance.

Dyes having similarly good properties are obtained by using (instead of 3-B-carbomethoxyethylmercapto-5- aminothiazole) S-B-carboethoxy-(or -propoxy-or -butoxy-)- ethylmercaptoSaminothiadiazole and following the procedure of example 1.

When the coupling components specified in the following table are used instead of the coupling component (N-benzyl- N-B-carboethoxyethylaniline) specified in example 1 and the procedure described in example I, is followed in other respects, dyes having similarly good properties are obtained.

HN-C 01m Example Shade of dyeing No. Coupling component on polyester 5 GET-C6115 Ruby.

C|H4C O 0 CH3 NHCOGH! 6 CHr-CeHs Red.

CzHaC O O C|H7 7- CHr-CQH; Red.

CzH|C O O 04H!) 8 /CH:CeHi Dark red.

CzHC O O OH H:

9..... OHi-CGHE Scarlet.

l CzHr-COOCzHt 10"... OCH; Violet.

CHr-CoHu 0211 C O O CH HNGOCH; 3

11 GET-OOH; Red.

C5H|C O 0 CH! 12......... /CH1C9H5 Ruby.

OzH|C O O CH;

13.. CQHICQHQ Scarlet.

021140 0 O CIHB Br ';We claim:

1. a water-insoluble monoazo dye having the formula:

Y ale- 1 in which R and R denote alkyl of one to four carbon atoms, X denotes hydrogen, methoxy, ethoxy, Y denotes hydrogen, chlorine or bromine, or methyl, ethyl, methoxy, ethoxy, acetylamino or propionylamino and n denotes one of the integers l and 2.

2. I} dye having the forrnt la;

in which Z denotes hydrogen, chlorine, or methyl and R, R and n have the meanings given in claim 1.

i A A d pate:

Taber 16,

Dated 7T1 Li smd that said Letters Patent are hereby ce'srectvad as ShOV 1 celow read L :mc;

J (I /Lam I 4 ormula rea Hans Guencer Erwin Han in cla I :54: \w/ E} It is certifiefi that error appears 1 "Patent No.

invantoria) Column 2,

Coluz'n should 

2. A dye having the formula: 